This invention is directed to a surfactant comprising a carbohydrate group. More particularly, the invention is directed to a surfactant comprising a carbohydrate group that results in superior cleaning properties in a dry cleaning system.
In many cleaning applications, it is desirable to remove contaminants (e.g., stains) from substrates, like metal, ceramic, polymeric, composite, glass and textile comprising substrates. Particularly, it is highly desirable to remove contaminants from clothing whereby such contaminants include dirt, salts, food stains, oils, greases and the like.
Typically, dry-cleaning systems use organic solvents, like chlorofluorocarbons, perchloroethylene and branched hydrocarbons to remove contaminants from substrates. In response to environmental concerns, other dry-cleaning systems have been developed that use inorganic solvents, such as densified carbon dioxide, to remove contaminants from substrates. The systems that use carbon dioxide to remove contaminants from substrates generally employ a surfactant and a polar co-solvent so that a reverse micelle may be formed to trap the contaminant targeted for removal.
In view of the environmental concerns associated with dry cleaning in, for example, halogenated hydrocarbons, many cleaning establishments have expressed their interests in cleaning with continuous phase solvents that comprise densified gases such as densified carbon dioxide as well as a biodegradable functionalized hydrocarbon or a silicon comprising solvent. Unfortunately, however, cleaning with such solvents is not made easy because only very few surfactants are compatible with such continuous phases.
It is of increasing interest to develop surfactants that enhance cleaning in a system that uses a densified gas, functionalized biodegradable hydrocarbon and/or a silicon comprising solvent. This invention, therefore, is directed to a surfactant comprising a carbohydrate group that unexpectedly results in superior cleaning properties in a dry cleaning system that utilizes a densified gas, a functionalized biodegradable hydrocarbon and/or silicon comprising solvent.
Efforts have been disclosed for dry cleaning with carbon dioxide. In U.S. Pat. No. 5,676,705, a superior dry cleaning method which employs densified carbon dioxide is described.
Other efforts have been disclosed for dry cleaning with carbon dioxide. In U.S. Pat. No. 5,683,473, a superior method for dry cleaning fabrics with a surfactant having a polysiloxane, branched polyalkylene oxide or halocarbon group is described.
Still further, U.S. Pat. No. 5,683,977 discloses a superior dry cleaning system with carbon dioxide and a surfactant adjunct.
Finally, in U.S. Pat. No. 5,866,005, a cleaning process using carbon dioxide as a solvent along with molecularly engineered surfactants is described.
None of the references above describe the use of surfactant comprising a carbohydrate group and a hydrocarbon group wherein the hydrocarbon group is more soluble in the dry cleaning solvent than the carbohydrate group.
In a first embodiment, the present invention is directed to a dry cleaning system comprising a surfactant comprising a hydrocarbon group which is solvent-philic and a carbohydrate group which is less solvent-philic than the hydrocarbon group.
In a second embodiment, the present invention is directed to a dry cleaning system comprising a dry cleaning solvent, and a surfactant or mixture of surfactants having the formula:
AXBxe2x80x83xe2x80x83I
wherein
(i) A is a moiety which is more soluble in the dry cleaning solvent than B; 
xe2x80x83a divalent group comnprising P or 
(iii) B is a carbohydrate group,
(iv) Z is H, or a C1-10alkyl group, or 
and G is a C1-6 alkyl,
(v) m is an integer from 0 to about 10, and d is 0 when m is 0 and 1 when m is xe2x89xa71,
with the proviso that A is not a siloxane, a halocarbon or a polyalkylene oxide.
In a third embodiment, the present invention is directed to a method for dry cleaning using the dry cleaning system of the first or second embodiment of the present invention.
Carbohydrate group, as used herein, is defined to mean a carbohydrate having at least one bond to an ester, ether, amine group, amide group, or divalent group comprising P. A divalent group comprising P is meant to mean a group derived from phosphine or phosphate.
There generally is no limitation with respect to the surfactant used in this invention as long as the surfactant will enhance cleaning in a system which utilizes a continuous phase solvent comprising a densified gas, biodegradable functionalized hydrocarbon, a silicon comprising solvent, or a mixture thereof.
Often, however, the surfactants which may be used in this invention have A as a C3 to C15 alkyl group (preferably a C8 to C10 alkyl group), or an aryl group; B as a monosaccharide or disaccharide, and preferably, not a polysaccharide. In the structure, X is an ester, ether, or amine group, and preferably, an ester group.
Regarding the carbohydrate group, the only limitation with respect to the carbohydrate group is that the carbohydrate group is less soluble in the dry cleaning solvent than A. Such a carbohydrate group may be selected from the group consisting of glucose, fructose, sucrose, galactose, lactose, ribose, lyxose, allose, altrose, erythrose, talose and mannose, including derivatives and disaccharides prepared therefrom.
When preparing the surfactant described in the present invention, conventional reactions, like those involving carboxylic acids and alcohol groups (esterifications); alkyl halides and alkoxides (Williamson ether synthesis); and reduction reactions involving ketones and primary amines (amine synthesis), may be used to produce the desired surfactant.
It is also noted herein that the surfactants which may be used in this invention are not limited with respect to where the moiety represented by A is bonded, via the group represented by X, to the carbohydrate group. Therefore, the moiety represented by A may be bonded (via the group represented by X) to a carbon within the carbohydrate ring or a group pendant to the carbons which make up the carbohydrate ring. Moreover, the surfactant employable in the present invention can include those which display carbohydrate ring opening after the moiety represented by A is attached to the carbohydrate ring by the group represented by X. Such a surfactant may also include a dimeric or trimeric surfactant generated from AXB R monomers. A preferred dimeric surfactant is 1,4-bis-[6-O-(n-octyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosid)]succinate. It is also noted herein that microorganism may be the source of the surfactants represented by AXB. Thus, surfactants which are classified as biosurfactants or microbial surfactants may be used in the dry cleaning system of the present invention.
A more detailed description of the types of surfactants comprising a carbohydrate group which may be used in this invention may be found in Colloids and Surfaces A: Physicochemical and Engineering Aspects, 102 (1995) 91-97, entitled xe2x80x9cNon-ionic Sugar-Based Surfactants: Self Assembly and Air/Water Interfacial Activityxe2x80x9d by Soderberg et al.; Langmuir 1997, 13, 6857-6860, entitled xe2x80x9cNonionic Boloamphiphiles and Gemini Surfactants Based on Carbohydratesxe2x80x9d by Pestman et al.; Langmuir 1999, 15, 2009-2014, entitled xe2x80x9cThermodynamics of Micellization of Nonionic Saccharide-Based N-Acyl-N-Alkylaldosylamine and N-Acyl-N-Alkylamino-1-deoxyalditol Surfactantsxe2x80x9d by Pestman et al.; Langmuir 2001, 17, 1941-1949, entitled xe2x80x9cStudies of N-Docecyllacto-bionamide, Maltose 6xe2x80x2-O-Dodecanoate, and Octyl-P-glucoside with Surface Tension, Surface Force, and Wetting Techniquesxe2x80x9d by Kjellin et al.; Biosurfactants and Biotechnology, pages 21-41, (1987) by Marcel Dekker, Inc., and Tetrahedron 55 (1999) 12711-12722, entitled xe2x80x9cNew Dimeric Surfactants from Alkyl Glucosidesxe2x80x9d by Castro et al., the disclosures of which are all incorporated herein by reference. Additional surfactants which may be used in this invention are described in World Patent Application Nos. 95/19951; 95/19953; 95/19954; 95/20026, the disclosures of which are incorporated herein by reference.
In a preferred embodiment, the surfactant comprising a carbohydrate group which may be employed in this invention has an HLB of less than 13; and preferably, less than about 12; and most preferably, less than about 10. In a most preferred embodiment, the surfactant comprising a carbohydrate group which may be used in this invention is an alkyl glucoside with A as a C8-10 alkyl group, B as a glucose group and X as an ester group, wherein A is joined to B via X and not at a carbon which is part of the glucose ring. Such a most preferred surfactant is sold under the name Triton CG-110 and made commercially available by the Union Carbide Corporation.
There generally is no limitation with respect to the continuous phase solvent (i.e., fluid) which may be employed with the surfactants described herein other than that the solvent is a densified gas (e.g., fluid which is a gas at standard temperature and pressure), a biodegradable hydrocarbon or a silicon comprising solvent, and capable of being a continuous phase in a dry cleaning application. Illustrative examples of the types of solvents which may be employed in this invention include a C2-C4 substituted or unsubstituted alkane, carbon dioxide, silicone oil, and an azeotropic solvent.
Regarding the solvent which is a densified gas, such a solvent may be, within the dry cleaning composition or process, a gas, liquid or supercritical fluid depending upon how densified the solvent is (how much pressure is applied at a given temperature) in the domestic or commercial cleaning application the solvent is used in. Propane and carbon dioxide tend to be the preferred solvents when the solvent selected is one which is a densified gas. Carbon dioxide, however, is especially preferred.
As to the silicon comprising solvent which may be used in this invention, such a solvent is typically a commercially available cyclic-siloxane based solvent made available from GreenEarth Cleaning, LLC. Such a solvent is generally one which has a flash point over about 65xc2x0 C., with octamethyl-cyclotetrasiloxane and decamethylcyclopentasiloxane being most preferred. A more detailed description of such conventional siloxane comprising solvents may be found in U.S. Pat. No. 5,942,007, the disclosure of which is incorporated herein by reference.
Especially preferred silicon comprising solvents are those having the formula: 
wherein each R is independently a substituted or unsubstituted linear, branched or cyclic C1-10 alkyl, C1-10 alkoxy, substituted or unsubstituted aryl, aryloxy, trihaloalkyl, cyanoalkyl or vinyl group, and R1 is a hydrogen or a siloxyl group having the formula:
Si(R2)3xe2x80x83xe2x80x83III
and each R2 is independently a linear, branched or cyclic C1-10 substituted or unsubstituted alkyl, C1-10 alkoxy, substituted or unsubstituted aryl, trihaloalkyl, cyanoalkyl, vinyl group, amino, amido, ureido or oximo group, and R1* is an unsubstituted or substituted linear, branched or cyclic C1-10 alkyl or hydroxy, or OSi(R2)3 whereby R2 is as previously defined, and e is an integer from about 0 to about 20.
The most preferred linear siloxane solvent is one wherein each R is methyl, R1 is Si(R2)3, R2 is methyl and R1* is methyl. Preferably, e is an integer from about 0 to about 10, and most preferably, an integer from about 2 to about 5.
Such solvents are made commercially available by General Electric, and Dow Corning under the name Dow Corning 200(R) fluid. A description of the solvents may be found in U.S. Pat. Nos. 3,931,047 and 5,410,007, the disclosures of which are incorporated herein by reference.
The biodegradable functionalized hydrocarbon that may be used in this invention includes those generally classified as an azeotropic solvent. Such an azeotropic solvent often comprises alkylene glycol alkyl ethers, like propylene glycol tertiary-butyl ether, and is described in U.S. Pat. No. 5,888,250, the disclosure of which is incorporated herein by reference. Moreover, as used herein, biodegradable functionalized hydrocarbon is defined to mean a biodegradable hydrocarbon comprising at least one member selected from the group consisting of an aldehyde, ketone, alcohol, alkoxy, ester, ether, amine, amide and sulfur comprising group.
When dry cleaning, for example, fabrics, like clothing or garments, with a solvent that is a densified gas (and the surfactants of this invention), the machine which is employed for cleaning is well known in the art. Such a machine typically comprises a gas supply, cleaning tank and condenser. The machine may further comprise a means for agitation. The means for agitation may be, for example, a mechanical device like a mechanical tumbler, or a gas-jet agitator. The art recognized machines which may be used in this invention (e.g., when a densified gas is used) may be found in U.S. Pat. Nos. 6,012,307, 5,943,721, 5,925,192, 5,904,737, 5,412,958, 5,267,455 and 4,012,194, the disclosures of which are incorporated herein by reference. Other machines employable in the present invention are made commercially available by Alliance Laundry Systems.
When dry cleaning for example, fabrics, like clothing or garments, with the biodegradable functionalized hydrocarbons or silicon comprising solvents and the surfactants described in this invention, the type of machine that may be used for the dry cleaning process is the same or substantially the same as the commonly used dry cleaning machines used for dry cleaning with perchloroethylene. Such machines typically comprise a solvent tank or feed, a cleaning tank, distillation tanks, a filter and solvent exit. These commonly used machines are described, for example, in U.S. Pat. No. 4,712,392, the disclosure of which is incorporated herein by reference.
When the fabric is placed in the machine and the continuous phase solvent of choice is fed into the machine, the normal cleaning cycle is run (typically between ten (10) minutes and one (1) hour). Prior to or after the start of the cleaning cycle, the surfactant comprising a carbohydrate group of this invention is introduced into the cleaning machine. Any of the surfactant represented by formula AXB may be used, including any mixture of surfactants thereof as well as dimeric or trimeric products thereof. Often, the amount of surfactant employed is from about 0.001 to about 15.0%, and preferably, from about 0.01 to about 5.0%, and most preferably, from about 0.01 to about 3.0% by weight of surfactant, based on total weight of surfactant and continuous phase solvent, including all ranges subsumed therein.
In addition to continuous phase solvent and the surfactant described in this invention, it is especially preferred to add from about 0.01% to about 10.0%, and preferably, from about 0.03 to about 3.0%, and most preferably, from about 0.05 to about 0.3% by weight of a polar additive (e.g., C1-10 alcohol and preferably water) based on total weight of continuous phase solvent, surfactant and polar additive, including all ranges subsumed therein. The addition of polar additive to the continuous phase solvent and surfactant is often desired so that cleaning may be enhanced, for example, by the formation of reverse micelles.
When cleaning fabrics, for example, with the surfactants of this invention, the pressure and temperature of the dry cleaning system (e.g., the system comprising the fabric targeted for cleaning, the continuous phase solvent and the surfactant described in this invention) within the machine is limited only to the extent that the temperature and pressure allow for the fabric to be cleaned. The pressure is often from about 14.7 to about 10,000 psi, and preferably, from about 200 to about 5,000 psi, and most preferably, from about 250 to about 3,000 psi, including all ranges subsumed therein. The temperature is often from about xe2x88x9230.0 to about 100xc2x0 C., and preferably, from about xe2x88x925.0 to about 70.0xc2x0 C., and most preferably, from about 0.0 to about 45xc2x0 C., including all ranges subsumed therein.
It is also noted herein that optional additives may be employed when cleaning with the surfactants described in this invention. Such optional additives include an oxidizing agent, like hydrogen peroxide, and an organic bleach activator such as those represented by the formula: 
wherein n is an integer from about 0 to about 20 and X1 is hydrogen or SO3M and M is hydrogen, an alkaline metal or an immodium cation. A more detailed description of such additives may be found in U.S. Pat. No. 5,431,843, the disclosure of which is incorporated herein by reference.
Other optional additives that may be employed to clean with the surfactants described in this invention include anti-static agents and deodorizing agents. Such anti-static agents typically include C8-C12 alcohol ethoxylates, C8-C12 alkaline glycols and glycol esters. The deodorizing agent, on the other hand, typically includes fragrances such as those described in U.S. Pat. No. 5,784,905, the disclosure of which is incorporated herein by reference.
Still other optional additives include viscosity modifiers like propylene glycol and sodium xylene sulphonate. As to the amount of optional additives used with the surfactants of the present invention, such an amount is limited only to the extent that the additive does not interfere with the cleaning process.